Coating compound



Patentecl July 16, 1940 UNITED STATES PATENT OFFICE COATING COMPOUND Arthur W. Johnson and George H. Young, Pittsburgh, Pa., assignors to Stoner-Mudge, Inc., a corporation of Pennsylvania No Drawing. Application-July 28, 1938,

, Serial No. 221,799

6 Claims. 260-86) In UnitedStates Letters Patent No. 2,130,924, apoquinine, quinidine, cinchonine, cinchonidine, we have described and claimed a thermally staquinoidine, cinchona febrifuge, and crude apobilized coating compound. The compound is dequinine bases. This, he says, exhausts the fined as consisting primarily of certain of those list of readily available cinchona alkaloids. I

resinous polymeric vinyl compounds known comhave found none, he adds, that is not servicemercially as Vinylite. The compound, it is exable to achieve thermal stabilization, and my plained, are the polymers and co-polymers of experimentation indicates that all of the cinvarious vinyl compounds, such polymers and cochona alkaloids, pure and impure, single and polymers being of resinous nature; andamong mixed, are so serviceable.

them a typical list includes polyvinyl acetate, The formula for quinoline, a typical substance polyvinyl propionate, polyvinyl chloride, polyvinyl of the first application, is bromide, polyvinyl chloro-bromide, polyvinyl n chloro-acetate, polyvinyl chloro-propionate, and polyvinyl chloro-alcohol; and the general char- HC 0 on 16 acterization is any polymer, co-polymer or poly- 4, 3,, u

meric mixture of the compound responding to v the formula CHz=CH--X, in which X may be S; N a halogen, the hydroxyl group, acetoxyl, propiom The f l for quinine is oxyl, or in general, any monocarboxylic acyloxyl Y N n H on i 20 group' o c c-wf, CHz

The substance that, added to Vinylite, affords H I improved thermal stability, is, according to the -f? C H disclosure of the application named, fa pitch con- BC on /H taining one or more of the tar bases which boil at temperatures higher than 240 C. at atmospheric H 25 pressure? Thesgtar bases may be added"e1 ther Our further investigations have revealed the as isolated Product? m the form of a purified fact that yet other substances will similarly serve pitchy WaXFmtainmg the basesin the form as thermal stabilizers for Vinylite. We have of a'crude pltch Among specific substances found that the ring-substituted pyridines, for

cessfully used, coal tar pitch, natural asphalt, instance o S r The f m 1 30 bone pitch, and water-gas pitch, and, additionis 1 s e V mm a for pyr dme ally, technical quinoline are named.

H In consequence of improved thermal stability, C a protective film of the coating compound of the application may be subjected to baking at ing I v 35 creased temperatures, and as a result a marked improvement in cohesion to the surface being N coated, and in resistance to moisture and other and th pyridine derivatives, or, in common parcorrosive influences, is efiected. Also as applied lance, the pyridines include compounds of a, B,

to a metal, the metal coated with a Vinylite film 7 or afi, and a'fi' ty e, according as one or more 40 of increased t e a Stability s p as a of the hydrogen atoms suffers displacement.

m te al article, of being subjected to tcm- We have observed a common characteristic of D of increased Severity W t cs rll all these stabilizing substances to be that all in-, tion of e coating thereon. clude nitrogen in ring formation, the double-bond In Unit d S a Letters Patent of the nitrogen within the ring being conjugated 45 one of us has described and claimed a thermally with a doub1e bond not within the ring, That is stabili d coating mp n t at nsis s of to say, with attention confined to the pyridines, the S me ate Vinylitc, S a i ed by the all conform to aschematic formula, not intended addition of other particular material. The stato how valency considerations bilizer of this second application is described as H 50 a compound selected from the class known as 0 r the quinoline and isoquinoline bases, and particularly from the 'cinchona alkaloid bases. The H applicant says that he has used quinine with success, and also isoquinine, hydroquinine, ethyl 55 g in which the component X==Y is a component of double-bond linkage, and this double-bond linkage is conjugate with'the double-bond nitrogen within the ring.

In all of the instances given the following conjugation persists I The pyridines include them substituted, the :5 substituted, and the ot'fl' substituted pyridines (the last named being the benzo-pyridines, or quinolines). The formula for a styryl pyridine is HC/ \CH l l H H H -o=cc N in (3H HO on And in this formula the hydrogen atom of either the o, m, or p positions or the hydrogen atoms of both 0 and o, the p, or the m and m positions in the benzene ring may be replaced by the hydroxyl group, or by chlorine, bromine, or iodine. In addition, we have found the pyridyl ethylenes serviceable, among which a-pyridyl ethylene will serve as an example. Its formula is So iso-pyrophthalone will serve. Its formula is l J l We have then found that substances generally of the class of heterocyclic nitrogen bases are serviceable, in which the ring includes a doublebonded nitrogen conjugated) with a double bond not Within the ring. In the schematic formula- X may be any trior tetra-valent element capable of forming a double-bonded linkage (typically C or N) and Y may be typically C, N, or O; and, as has been seen the elements C or N, or C, N. or 0, so situated, may, in tiun, be linked in other groups of greatest diversity and variety.

We have found no substance so characterized that does not have in the association described the stabilizing effect indicated.

From these particular instances and generalizations We have advanced in the progress of our discovery to a yet wider field of generalization.

We have found that by adding, to the resinous polymeric vinyl compound specifically named above, compound selected from the class consisting the heicrocyclic nitrogen bases containing 3llt-ifhillll substituents having at least double bond which is conjugated with respect to a double-bonded nitrogen in the parent heterocyclic em, an applied coating of the mix I-lli'e es greatly increased thermal sta- In the above formula N is nitrogen; X may be any trior tetra-valent element capable of entering into a double-bonded system, and typically may be carbon or nitrogen; Y may be any di-, tri-, or tetra-valent element capable of entering into a double-bonded system together with X, and typically may be carbon, nitrogen, or oxygen. R', R", R' and R may be simply hydrogen, or any other aliphatic or aromatic hydrocarbon radical; similarly, R and R", and

v R and R"" may be joined together by chemical bonds to form a condensed ring system; also R" and Y may be joined together to form a condensed ring system, except in the special case when Y is oxygen. Further, A, B, D, E, and F typically may be carbon atoms, or one or more may be another element, (such as nitrogen) capable of entering into a ring system and of bonding to side chains shown in the above generalized formula as R, R", R', and R"". In a special case, oxygen or sulphur may be a member of the ring, in which case there will be no attached side group on that atom.

Specifically, we mean compounds of the pyridine, quinoline, and isoquinoline type, of the acridine type, of the pyrazine type, of the pyrazole type, of the thio pyrazole type, or (in general) heterocyclic. bases containing at least one doublebonded ring nitrogen conjugated with a double bond outside the parent ring. Exemplary of compounds of pyrazine type are quinoxaline and (1) To 100 grams of the resinous vinyl compound described above are added 2 grams of tripyridyl, and the whole brought into solution in a mixture consisting of 4 parts of methyl isobutyl ketone and 1 part of toluol, the total con- Ccniration of solids being typically 20 per cent by weight of the Whole. This stabilized coating compound may be spread upon tin plate, for example, at the usual coating thicknesses and thereafter baked at temperatures approximating 350 F. without noticeable thermal decomposition.

(2) To 100 grams of the resinous vinyl compound described above, suitably dispersed in a solvent mixture consisting of 3 parts methyl ethyl ketone, 1 part of methyl isobutyl ketone, and 1 part of toluol, at a concentration of 20 per cent solids. is added 1 gram of isopyrophthalonc.

This stabilized coating compound may be spread (8) To grams of the resinous vinyl com pound described above, and dispersed in a suitable solvent mixture such as is described under Example 2, are added 2 grams of alpha pyridyl o-hydroxy phenyl ethylene. This stabilized coating compound may be spread upon tin-plate, for example, and thereafter baked at temperatures approximating 350 F. without noticeable thermal decomposition. 1

(4) To 100 grams of the resinous vinyl compound described above are added 2 grams of stilbazole, andthe whole is then dispersed in a suitable solvent mixture such as is described under Example 1. This stabilized coating compound may be spread upon iron, for example, and thereafter baked at temperatures approximating 325 F. without noticeable thermal decomposition.

(5)- To 100 grams of the resinous vinyl compound described above are added 2 grams of alpha pyridyl furyl ethylene, and the whole is then dispersed in a suitable solvent mixture such as is described under Example 2. Thissta-bilized coating compound may be spread upon copper, for example, and thereafter baked at tempera tures approximating 380 F. without noticeable thermal decomposition.

(6) To 100 grams of the resinous vinyl compound described above are added 2 grams of alpha pyridyl, o-chlorophenyl ethylene, and the whole is then dispersed in a suitable solvent mixture such as is describedunder Example 1.

This stabilized coating compound may be spread upon zinc, for example, and thereafter baked at temperatures approximating 300 F. without noticeable thermal decomposition.

(7) To 100 grams of the resinous vinyl compound described above are added 2 grams of alpha benzopyridyl-p-chlorophenyl. ethylene and the whole is then dispersed in a suitable solvent mixture such as is described under Example 1. This stabilized coating compound may be spread upon zinc, for example, and thereafter baked at temperatures approximating 300 F. without noticeable thermal decomposition,

(8) To 100 grams of the resinous vinyl compound described above are added 0.5 gram of quinicine,and the whole is then dispersed in a suitable solvent mixture such as is described under Example 2.

and thereafter baked at temperatures approximating 360 F. without noticeable thermal decomposition.

ene, and the whole is then dispersed in a suit-.

able solvent such as so described under Example 2. This stabilized coating compound may be spread upon iron, for example, and thereafter This stabilized coating cornpound may be spread upon tin-plate, for example,

baked at temperatures approximating 325 F. without noticeable thermal decomposition.

(11) To 100 grams of the resinous vinyl compound described above may be added 2 grams of alpha pyrazol-o-hydroxy phenyl ethylene, and the whole'is then, dispersed in a suitable solvent such as is described under Example 2. This stabilized coating compound may be spread upon iron, for example, and thereafter baked at temperatures approximating 325 F. without noticeable thermal decomposition.

We claim as our invention:

1. A thermally stabilized coating compound consisting of a polymer of a substance responding to the formula CH2=CHX, in which X is selected from a group consisting of the halogens,

the hydroxyl group, and the monocarboxylic acyloxyl groups, and a thermal stabilizer consisting of a heterocyclic nitrogen base selected from the group consisting of a-pyridyl-o-chlorophenyl ethylene, tripyridyl, isopyrophthalone, alpha .pyridyl-o-hydroxy phenyl ethylene, stilbazole, alpha pyridyl furyl ethylene, alpha benzopyridyl-p-chlorophenyl ethylene, quinicine, cinchonocine, alpha benzo-pyridyl-o-p-dihydroxy phenyl ethylene, alpha pyrazol-o-hydroxy phenyl ethylene, and their basic derivatives and homologs, such stabilizer. being present in a ratio not to exceed 5 parts by weight of stabilizer to 100.

parts of the first named substance.

2. A thermally stabilized coating compound consisting of a polymer of a substance responding to the formula CH2=CHX, in which X is a substance of an association consisting of the halogens, the hydroxyl group, and the monocarboxylic acyloxyl groups, and a stabilizer con sisting of isopyrophthalone.

3.- A thermally stabilizedcoating compound consisting of a conjoint polymer of vinyl chloride and vinyl acetate, and a stabilizer consisting of a heterocyclic nitrogen base selected from the group consisting of a-pyridyl-o-chlorophenyl ethylene, tripyridyl, isopyrophthalone, alpha pyridyl-o-hydroxy phenyl ethylene, stilbazole, alpha pyridyl furyl ethylene, alpha benzopyridylp-chlorophenyl ethylene, quinicine, c-inchonocine, alpha benzopyridyl-o-p-dihydroxy phenyl ethylene, alpha pyrazyl-o-hydroxy phenyl ethylene, and their basic derivatives and homologs, such stabilizer being present in a ratio not to exceed 5 parts by weight of stabilizer to 100 parts of the first named substance.

parts by weight of stabilizer to 100 parts of the first named substance, the whole being dispersed in a mixture of solvents.

6. A thermally stabilized coating compound consisting of polyvinyl chloride, and a stabilizer consisting of isopyrophthalone.

ARTHUR W. JOHNSON. GEORGE H. YOUNG. 

